The polymer composite is attractive as an energy storage electrode for sustainable and high-performance technologies due to its unique properties of battery and capacitor in one system, i.e., the redox reaction occurring simultaneously with the anion doping/de-doping of the conductive polymer with AlCl4− ionic species contained in the ionic liquid. The structure of the polymer films, their doping/de-doping mechanism and the stability in the ionic liquid were characterised by scanning electron microscopy and cyclic voltammetry and compared with films electro-polymerised on planar vitreous carbon. The typical granular and nano/micro-porous polymer structure observed on planar vitreous carbon was successfully replicated on the macro-porous reticulated vitreous carbon surface. The polymer films show approximately 45% higher capacity than films on planar substrates and similar efficient redox behaviour, proving that the material has hybrid battery-capacitor properties enhanced by the higher area per unit volume of reticulated vitreous carbon.